CN111454711A - Quantum dots, composition and cured layer using same, color filter and display device including cured layer, and method of manufacturing cured layer - Google Patents

Abstract

Disclosed are a quantum dot surface-modified with a specific compound, a non-solvent type curable composition, a cured layer using the composition, a color filter comprising the cured layer, a display device comprising the cured layer, and a method of manufacturing the cured layer. The quantum dot surface-modified with a specific compound of the present invention can be easily applied to all photocurable compositions, solvent-based thermosetting compositions, and non-solvent-based thermosetting compositions, and thus can have improved viscosity and optical characteristics and processability.

Description

Quantum dots, composition and cured layer using same, color filter and display device comprising cured layer, and method of manufacturing cured layer

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to and the benefit of Korean Patent Application No. 10-2019-0007594 filed in the Korean Intellectual Property Office on Jan. 21, 2019, the entire contents of which are incorporated herein by reference.

technical field

The present disclosure relates to a quantum dot, a curable composition including the quantum dot, a cured layer manufactured using the composition, a color filter including the cured layer, a display device including the color filter, and a method of manufacturing the cured layer.

Background technique

In the case of general quantum dots, the solvent for their dispersion is limited due to their hydrophobic surface features. Therefore, it is difficult to incorporate into polar systems such as binders or curable monomers.

For example, even where quantum dot ink compositions are actively studied, in the initial steps, the polarity is still relatively low and it is dispersible in the solvents used for curable compositions with a high degree of hydrophobicity. Therefore, it is difficult (eg, impossible) to increase the optical efficiency (eg, luminous) of the ink at a certain level because it is difficult to increase the quantum dots to 20 wt % or more based on the total amount of the composition. efficiency, quantum efficiency, etc.). Even if quantum dots are additionally added and dispersed to improve light efficiency, the viscosity is beyond the range (12 centipoise (cP)) capable of ink-jetting and processability may not be satisfied. That is, processability may be compromised when the viscosity of the quantum dot ink composition exceeds the range suitable for jetting inks (eg, 12 centipoise) due to the addition of additional quantum dots.

To achieve a viscosity range capable of jetting the ink, the method of reducing the ink solids content by dissolving 50% or more by weight of the solvent based on the total amount of the composition also provides satisfactory results in terms of viscosity. However, it can be considered a satisfactory result in terms of viscosity, but nozzle drying due to solvent volatilization, nozzle clogging, smaller layer loss over time after ink jetting can become more severe and difficult to control thickness after curing deviation. Therefore, it is difficult to apply it to an actual process.

Therefore, a non-solvent type quantum dot ink that does not contain a solvent is the most preferred form for practical process application. Current techniques for applying quantum dots themselves to solvent-borne compositions are currently somewhat limited.

Currently, the most preferred solvent-borne composition for practical processes is the quantum dots without surface modification (eg, ligand substitution) having a content of about 20 to 25 wt% based on the total amount of the solvent-borne composition. Therefore, it is difficult to improve the light efficiency and absorptivity due to viscosity limitation. At the same time, attempts have been made to reduce the quantum dot content and increase the content of light diffusing agents (scatterers) in other improvement directions, but this has also failed to solve the deposition problem and the low light efficiency problem.

SUMMARY OF THE INVENTION

An embodiment provides a surface-modified quantum dot with improved optical characteristics.

Another embodiment provides a non-solvent curable composition containing quantum dots.

Another embodiment provides a solvent-borne curable composition comprising quantum dots.

Another embodiment provides a cured layer made using the composition.

Another embodiment provides a color filter including a cured layer.

Another embodiment provides a display device including a color filter.

Another embodiment provides a method of making a cured layer.

The embodiment provides a quantum dot surface-modified with one of the compounds represented by Chemical Formula 1 to Chemical Formula 14 or a combination thereof.

[Chemical formula 1]

[Chemical formula 2]

[Chemical formula 3]

[Chemical formula 4]

[Chemical formula 5]

[Chemical formula 6]

In Chemical Formula 1 to Chemical Formula 6,

R ¹ to R ⁷ are each independently substituted or unsubstituted C1 to C10 alkyl or substituted or unsubstituted C6 to C20 aryl,

L ¹ to L ¹⁶ are each independently substituted or unsubstituted C1 to C10 alkylene, and

n1 to n7 are each independently an integer of 0 to 10.

[Chemical formula 7]

[Chemical formula 8]

[Chemical formula 9]

In Chemical Formula 7 to Chemical Formula 9,

R ⁸ and R ⁹ are each independently substituted or unsubstituted C1 to C10 alkyl,

L ¹⁷ to L ²³ are each independently substituted or unsubstituted C1 to C10 alkylene, and

n8 to n10 are each independently an integer of 0 to 10.

[Chemical formula 10]

[Chemical formula 11]

[Chemical formula 12]

[Chemical formula 13]

In Chemical Formula 10 to Chemical Formula 13,

R ¹⁰ to R ¹⁵ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ²⁴ to L ²⁹ are each independently substituted or unsubstituted C1 to C10 alkylene, and

n11 to n16 are each independently an integer of 0 to 10.

[Chemical formula 14]

In Chemical Formula 14,

R ¹⁶ to R ¹⁸ are each independently substituted or unsubstituted C1 to C10 alkyl,

L ³⁰ to L ³² are each independently substituted or unsubstituted C1 to C10 alkylene, and

n17 to n19 are each independently an integer of 0 to 10.

Quantum dots can have a maximum fluorescence emission wavelength of 500 nanometers to 680 nanometers.

Another embodiment provides a non-solvent curable composition comprising quantum dots and a polymerizable monomer having a carbon-carbon double bond at the terminal, and based on the total amount of the non-solvent curable composition, comprising 40 The polymerizable monomer in an amount of % to 80% by weight.

The polymerizable monomer may have a molecular weight of 220 g/mole to 1,000 g/mole.

The polymerizable monomer may be represented by Chemical Formula 15.

[Chemical formula 15]

In Chemical Formula 15,

R ¹⁹ and R ²⁰ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ³³ and L ³⁵ are each independently substituted or unsubstituted C1 to C10 alkylene, and

L ³⁴ is a substituted or unsubstituted C1 to C10 alkylene or ether group.

The non-solvent curable composition may further comprise a polymerization initiator, a light diffusing agent or a combination thereof.

The light diffusing agent is barium sulfate, calcium carbonate, titanium dioxide, zirconia, or a combination thereof.

The non-solvent curable composition may further comprise a polymerization inhibitor; malonic acid; 3-amino-1,2-propanediol; a silane-based coupling agent; a leveling agent; a fluorine-based surfactant or a combination thereof.

The quantum dots in the non-solvent-type curable composition may be quantum dots surface-modified with one of the compounds represented by Chemical Formula 1 to Chemical Formula 14 or a combination thereof.

Another embodiment provides a solvent-based curable composition including quantum dots, surface-modified with one or a combination of compounds represented by Chemical Formula 1 to Chemical Formula 14; a binder resin, and a solvent.

The solvent-based curable composition may further comprise a polymerizable monomer, a polymerization initiator, a light diffusing agent, or a combination thereof.

The solvent-based curable composition may be a photosensitive resin composition.

Another embodiment provides a cured layer made using the composition.

Another embodiment provides a color filter including a cured layer.

Another embodiment provides a method of making a cured layer, the method comprising applying a composition to a substrate by an ink jet method to form a pattern; and curing the pattern.

Another embodiment provides a method of making a cured layer, the method comprising applying a composition to a substrate by an ink jet method to form a pattern; developing the pattern; and thermally treating the result.

Other embodiments of the invention are included in the following detailed description.

One embodiment provides a quantum dot surface-modified with a specific compound, and compared with conventional quantum dots, the surface-modified quantum dots can be easily applied to all photocurable compositions, solvent-based thermosetting compositions, and non-solvent-based thermosetting compositions composition, and thus may have improved viscosity and optical characteristics and processability.

Detailed ways

Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, the present invention is not limited thereto and the present invention is defined by the scope of the claims.

As used herein, when no specific definition is otherwise provided, "alkyl" refers to C1 to C20 alkyl, "alkenyl" refers to C2 to C20 alkenyl, and "cycloalkenyl" refers to C3 to C20 cycloalkene group, "heterocycloalkenyl" refers to C2 to C20 heterocycloalkenyl, "aryl" refers to C6 to C20 aryl, "aralkyl" refers to C6 to C20 aralkyl, "alkylene" is refers to C1 to C20 alkylene, "arylene" refers to C6 to C20 arylene, "alkylarylene" refers to C6 to C20 alkylarylene, "heteroarylene" refers to C3 to C20 C20 heteroarylene, and "alkyleneoxy" refers to C1 to C20 alkyleneoxy.

As used herein, when no specific definition is otherwise provided, "substituted" refers to the replacement of at least one hydrogen atom by a substituent selected from the group consisting of halogen atoms (F, Cl, Br or I), hydroxyl, C1 to C20 Alkoxy group, nitro group, cyano group, amino group, imino group, azide group, formamidinyl group, hydrazine group, hydrazono group, carbonyl group, carbamoyl group, thiol group, ester group, ether group, carboxyl group or its salt , sulfonic acid group or its salt, phosphoric acid or its salt, C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C6 to C20 aryl, C3 to C20 cycloalkyl, C3 to C20 cycloalkenyl , C3 to C20 cycloalkynyl, C2 to C20 heterocycloalkyl, C2 to C20 heterocycloalkenyl, C2 to C20 heterocycloalkynyl, C3 to C20 heteroaryl, or combinations thereof.

As used herein, when no specific definition is otherwise provided, "hetero" refers to inclusion of at least one heteroatom of N, O, S, and P in a chemical formula.

As used herein, when a specific definition is not otherwise provided, "(meth)acrylate" refers to both "acrylate" and "methacrylate", and "(meth)acrylic" refers to "acrylic acid" " and "methacrylic acid".

As used herein, when no specific definition is otherwise provided, the term "combination" refers to mixing or copolymerization.

As used herein, when a definition is not otherwise provided, a hydrogen bond is in a position where a chemical bond should exist but is not drawn in a chemical formula.

As used herein, a cardo-based resin refers to a resin including at least one functional group selected from Chemical Formula 16-1 to Chemical Formula 16-11 in the main chain of the resin.

In addition, in the present specification, when no definition is otherwise provided, "*" refers to a bonding point to the same atom or chemical formula or to a different atom or chemical formula.

The quantum dots according to an embodiment may be quantum dots surface-modified with a compound having a polar group (ie, a compound having a high affinity for a polymerizable monomer having a carbon-carbon double bond at the terminal). In the case of the surface-modified quantum dots described above, it is very easy to produce a highly concentrated or highly concentrated quantum dot dispersion (improving the dispersibility of quantum dots to monomers), thereby realizing a non-solvent type curable composition and Greatly improved light efficiency.

For example, a compound having a polar group may have a structure that has a high affinity for the chemical structure of a monomer including a compound having a carbon-carbon double bond.

For example, the compound having a polar group may be represented by one of Chemical Formula 1 to Chemical Formula 14, but is not necessarily limited thereto.

[Chemical formula 1]

[Chemical formula 2]

[Chemical formula 3]

[Chemical formula 4]

[Chemical formula 5]

[Chemical formula 6]

In Chemical Formula 1 to Chemical Formula 6,

R ¹ to R ⁷ are each independently substituted or unsubstituted C1 to C10 alkyl or substituted or unsubstituted C6 to C20 aryl,

L ¹ to L ¹⁶ are each independently substituted or unsubstituted C1 to C10 alkylene, and

n1 to n7 are each independently an integer of 0 to 10.

[Chemical formula 7]

[Chemical formula 8]

[Chemical formula 9]

In Chemical Formula 7 to Chemical Formula 9,

R ⁸ and R ⁹ are each independently substituted or unsubstituted C1 to C10 alkyl,

L ¹⁷ to L ²³ are each independently substituted or unsubstituted C1 to C10 alkylene, and

n8 to n10 are each independently an integer of 0 to 10.

[Chemical formula 10]

[Chemical formula 11]

[Chemical formula 12]

[Chemical formula 13]

In Chemical Formula 10 to Chemical Formula 13,

R ¹⁰ to R ¹⁵ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ²⁴ to L ²⁹ are each independently substituted or unsubstituted C1 to C10 alkylene, and

n11 to n16 are each independently an integer of 0 to 10.

[Chemical formula 14]

In Chemical Formula 14,

R ¹⁶ to R ¹⁸ are each independently substituted or unsubstituted C1 to C10 alkyl,

L ³⁰ to L ³² are each independently substituted or unsubstituted C1 to C10 alkylene, and

n17 to n19 are each independently an integer of 0 to 10.

For example, the compounds represented by Chemical Formula 1 to Chemical Formula 14 may be represented by one of Chemical Formula A to Chemical Formula P, but are not necessarily limited thereto.

[Chemical formula A]

[Chemical formula B]

[Chemical formula C]

[chemical formula D]

In Chemical Formula D, m1 is an integer of 0 to 10.

[chemical formula E]

[chemical formula F]

[chemical formula G]

[chemical formula H]

[Chemical formula I]

[chemical formula J]

[Chemical formula K]

[chemical formula L]

[chemical formula M]

[chemical formula N]

[chemical formula O]

[chemical formula P]

Surface modification of quantum dots is easier with the use of specific compounds. If the quantum dots surface-modified with the aforementioned compounds are added to the aforementioned monomers and stirred, an extremely transparent dispersion liquid can be obtained, which is a measure to confirm that the quantum dots are well surface-modified.

For example, quantum dots can have a maximum fluorescence emission wavelength of about 500 nanometers to about 680 nanometers.

A non-solvent-based curable composition according to another embodiment comprises quantum dots and a polymerizable monomer, wherein the monomer is included in an amount of about 40 wt % to about 80 wt % based on the total amount of the non-solvent-based curable composition body.

Embodiments relate to a non-solvent curable composition comprising quantum dots. At present, curable compositions (inks) containing quantum dots have been developed to make thiol binders or monomers (resins for quantum dot flakes containing 4T, such as those with four Monomers of thiol groups)) are specialized and further commercialized.

On the other hand, since polymerizable monomers are generally and widely used, vinyl monomers (including vinyl-based monomers, acrylate-based monomers, methacrylate-based monomers, and monofunctional monomers or polyfunctional monomers) The analogs of ) have low compatibility with quantum dots and are limited in terms of quantum dot dispersibility, so their effective application to various developments of quantum dot-containing curable compositions is substantially difficult. In particular, vinyl monomers do not show high-concentration quantum dot dispersibility, and thus are difficult to apply to curable compositions containing quantum dots.

Due to this disadvantage, curable compositions containing quantum dots have been developed to have compositions containing substantial amounts (greater than or equal to about 50% by weight) of solvent, but when the solvent content is increased, ink jet processability may be degraded sex. Therefore, in order to satisfy ink jet processability, the demand for non-solvent curable compositions continues to increase.

In other words, one embodiment relates to the ever-increasing demand for non-solvent-based curable compositions that can have a passivation effect that does not degrade the intrinsic optical characteristics of quantum dots, and by increasing the total amount of curable compositions The inclusion of about 40 wt % to about 80 wt % by weight of a polymerizable monomer comprising a polymerizable monomer having at the terminus, even in a solvent-free system, provides a high concentration of dispersion of quantum dots together with quantum dots. Compounds of carbon-carbon double bonds, and thus improve the affinity of quantum dots for curable compositions.

Hereinafter, each component is specifically described.

[Quantum dots]

The quantum dots contained in the non-solvent curable composition may be quantum dots surface-modified with one of the compounds represented by Chemical Formula 1 to Chemical Formula 14 or a combination thereof, but are not necessarily limited thereto.

For example, quantum dots absorb light in the wavelength region of about 360 nanometers to about 780 nanometers (eg, about 400 nanometers to about 780 nanometers) and emit about 500 nanometers to about 700 nanometers (eg, about 500 nanometers to about 580 nanometers) Fluorescence in a wavelength region, or emission of fluorescence in a wavelength region of about 600 nanometers to about 680 nanometers. That is, the quantum dots may have a maximum fluorescence emission wavelength (λ _em ) of about 500 nanometers to about 680 nanometers.

The quantum dots can each independently have a full width at half maximum (FWHM) of about 20 nanometers to about 100 nanometers (eg, about 20 nanometers to about 50 nanometers). When the quantum dots have a full width at half maximum (FWHM) of the range, the color reproducibility increases when the quantum dots are used as a color material in a color filter due to high color purity.

The quantum dots may each independently be an organic material, or an inorganic material, or a mixture (mixture) of an organic material and an inorganic material.

The quantum dots may each independently consist of a core and a shell surrounding the core, and the core and the shell may each independently have the following structures: a core consisting of Group II to Group IV, Group III to Group V, and the like, Core/Shell, Core/First Shell/Second Shell, Alloy, Alloy/Shell, and the like, but not limited thereto.

For example, the core may comprise at least one material selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, GaN, GaP, GaAs, InP, InAs, and alloys thereof, but not necessarily limited to this. The shell surrounding the core may include at least one material selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, HgSe, and alloys thereof, but is not necessarily limited thereto.

In one embodiment, since the world has recently become more concerned about the environment and has also tightened the management of toxic materials, non-cadmium-based luminescence with little low quantum efficiency (quantum yield) but environmentally friendly is used. A material (InP/ZnS, InP/ZnSe/ZnS, etc.) replaces the light-emitting material having a cadmium-based core, but is not necessarily limited thereto.

In the case of quantum dots of a core/shell structure, the overall size (average particle size) including the shell may be about 1 nanometer to about 15 nanometers, eg, about 5 nanometers to about 15 nanometers.

For example, the quantum dots may each independently comprise red quantum dots, green quantum dots, or a combination thereof. The red quantum dots can each independently have an average particle size of about 10 nanometers to about 15 nanometers. The green quantum dots may each independently have an average particle size of about 5 nanometers to about 8 nanometers.

On the other hand, for the dispersion stability of quantum dots, the non-solvent curable composition according to an embodiment may further include a dispersant. The dispersing agent contributes to uniform dispersibility of the photoconversion material (eg, quantum dots) in the non-solvent-based curable composition, and may include a nonionic dispersing agent, an anionic dispersing agent, or a cationic dispersing agent. Specifically, the dispersant may be polyalkylene glycol or its ester, polyoxy alkylene, polyhydric alcohol ester alkylene oxide addition product, alcohol epoxy Alcohol alkyleneoxide addition products, sulfonates, sulfonates, carboxylates, carboxylates, alkylamide alkylene oxide addition products, alkylamines, and the like, alone or in combination of two or a mixture of more than two. The dispersant may be used in an amount of about 0.1 wt % to about 100 wt %, eg, about 10 wt % to about 20 wt %, relative to the solid content of the photoconversion material (eg, quantum dots).

Quantum dots, eg, surface-modified quantum dots, may be included in an amount of about 1 wt% to about 40 wt%, eg, about 3 wt% to about 30 wt%, based on the total amount of the non-solvent curable composition. When quantum dots (eg, surface-modified quantum dots) are included in the range, the light conversion rate can be improved without interfering with pattern characteristics and development characteristics, so that it can have excellent processability.

[Polymerizable monomer having carbon-carbon double bond at the terminal]

The monomer having a carbon-carbon double bond at the terminal may be included in an amount of about 40 wt % to about 80 wt % based on the total amount of the non-solvent curable composition. For example, the monomer having a carbon-carbon double bond at the terminal may be included in an amount of about 50 wt % to about 80 wt % based on the total amount of the non-solvent curable composition. When the monomer having a carbon-carbon double bond at the terminal is included in the range, a non-solvent curable composition having a viscosity capable of jetting ink can be prepared and the quantum dots in the prepared non-solvent curable composition can be Has improved dispersion, thereby improving optical characteristics.

For example, monomers having carbon-carbon double bonds at the termini can have molecular weights of about 220 grams/mole to about 1,000 grams/mole. When monomers with carbon-carbon double bonds at the ends have molecular weights in the range, it may be advantageous for jet inks because it does not increase the viscosity of the composition and does not hinder the optical characteristics of quantum dots.

For example, a monomer having a carbon-carbon double bond at the terminal may be represented by Chemical Formula 15, but is not necessarily limited thereto.

[Chemical formula 15]

In Chemical Formula 15,

R ¹⁹ and R ²⁰ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ³³ and L ³⁵ are each independently substituted or unsubstituted C1 to C10 alkylene,

L ³⁴ is a substituted or unsubstituted C1 to C10 alkylene or ether group (*-O-*).

For example, the monomer having a carbon-carbon double bond at the terminal may be represented by Chemical Formula 15-1 or Chemical Formula 15-2, but is not necessarily limited thereto.

[Chemical formula 15-1]

[Chemical formula 15-2]

For example, in addition to the compound of the aforementioned Chemical Formula 15-1 or Chemical Formula 15-2, the monomer having a carbon-carbon double bond at the terminal may further include ethylene glycol diacrylate, triethylene glycol diacrylate, 1 ,4-Butanediol Diacrylate, 1,6-Hexanediol Diacrylate, Neopentyl Glycol Diacrylate, Pentaerythritol Diacrylate, Pentaerythritol Triacrylate, Dipentaerythritol Diacrylate, Dipentaerythritol Triacrylate , dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, novolacepoxyacrylate, ethylene glycol dimethacrylate, triethylene glycol Dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, or a combination thereof.

In addition, along with the monomer having a carbon-carbon double bond at the terminal, common monomers of conventional thermosetting compositions or photocurable compositions may be further included. For example, the monomers further include oxetane-based compounds such as bis[1-ethyl(3-oxetanyl)]methyl ether and the like.

[Polymerization initiator]

The non-solvent curable composition according to an embodiment may further include a polymerization initiator, such as a photopolymerization initiator, a thermal polymerization initiator, or a combination thereof.

Photopolymerization initiators are commonly used initiators for photosensitive resin compositions, such as acetophenone-based compounds, benzophenone-based compounds, thioxanthone-based compounds Compounds, benzoin-based compounds, triazine-based compounds, oxime-based compounds, aminoketone-based compounds, and the like, but not necessarily limited thereto.

Examples of acetophenone compounds may be 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyl Trichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4- (Methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, and analog.

Examples of benzophenone compounds may be benzophenone, benzoyl benzoate, benzoyl methyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, Acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminodiphenyl Methanone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, and the like.

Examples of thioxanthones may be thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone , 2-chlorothioxanthone and the like.

Examples of benzoin compounds may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethylketal, and the like.

Examples of triazine compounds may be 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3', 4'-Dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl) Methyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis( Trichloromethyl)-s-triazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine oxazine, 2-(naphthol-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthol-yl)-4,6-bis(trichloromethyl) Methyl)-s-triazine, 2,4-bis(trichloromethyl)-6-sunenyl-s-triazine (2,4-bis(trichloromethyl)-6-piperonyl-s-triazine), 2 , 4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine and the like.

Examples of oxime-based compounds may be O-acyloxime-based compounds, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2- Octanedione, 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl -α-Oxyamino-1-phenylpropan-1-one and the like. Specific examples of O-acyl oximes may be 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-benzene yl)-butan-1-one, 1-(4-phenylthiophenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylthiophenyl)-butane-1,2-dione-2-oxime-O-benzoate Phenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylthiophenyl)-oct-1-one oxime-O-acetate, 1-(4-Phenylthiophenyl)-butan-1-one oxime-O-acetate and the like.

Examples of aminoketones may be 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one and the like.

In addition to the compounds, the photopolymerization initiator may further comprise carbazole-based compounds, diketone-based compounds, sulfonium borate-based compounds, diazo-based compounds, imidazole-based compounds, biimidazole-based compounds and the like .

Photopolymerization initiators can be used together with photosensitizers capable of causing chemical reactions by absorbing light and becoming an excited state, and then transferring its energy.

Examples of photosensitizers may be tetraethylene glycol bis-3-mercapto propionate, pentaerythritol tetrakis-3-mercapto propionate, dipentaerythritol Tetrakis-3-mercaptopropionate and the like.

Examples of thermal polymerization initiators can be peroxides, specifically, benzoyl peroxide, dibenzoyl peroxide, lauryl peroxide, dilauryl peroxide, di-tert-butyl peroxide base, cyclohexane peroxide, methyl ethyl ketone peroxide, hydroperoxides (e.g., tert-butyl hydroperoxide, cumene hydroperoxide), dicyclohexyl peroxydicarbonate, peroxybenzene t-butyl peroxybenzoate and/or the like; azo polymerization initiators such as 2,2-azo-bis(isobutyronitrile), 2,2'-azobis-2-methane propionitrile and/or the like, but the present disclosure is not necessarily so limited, and any suitable thermal polymerization initiator (eg, well known in the art) may be used.

The polymerization initiator may be included in an amount of about 0.1 wt % to about 5 wt %, eg, about 1 wt % to about 4 wt %, based on the total amount of the non-solvent curable composition. When the polymerization initiator is included in the range, excellent reliability can be obtained due to sufficient curing during exposure or thermal curing, and transmittance deterioration due to non-reactive initiators is prevented, thereby preventing quantum The optical characteristics of the dots are degraded.

[Light Diffuser (or Light Diffuser Dispersion)]

The non-solvent curable composition according to an embodiment may further include a light diffusing agent.

For example, the light diffusing agent may include barium sulfate (BaSO ₄ ), calcium carbonate (CaCO ₃ ), titanium dioxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), or a combination thereof.

The light diffusing agent can reflect light that is not absorbed in the aforementioned quantum dots, and cause the quantum dots to absorb the reflected light again. That is, the light diffusing agent can increase the amount of light absorbed by the quantum dots and improve the light conversion efficiency of the curable composition.

The light diffusing agent may have an average particle size ( _D50 ) of about 150 nanometers to about 250 nanometers, and particularly about 180 nanometers to about 230 nanometers. When the average particle size of the light diffusing agent is within the range, it can have better light diffusing effect and improve light conversion efficiency.

The light diffusing agent may be included in an amount of about 1 wt % to about 20 wt %, eg, about 5 wt % to about 10 wt %, based on the total amount of the non-solvent curable composition. When the light diffusing agent is included in an amount of less than about 1 wt % based on the total amount of the non-solvent-type curable composition, it is difficult to expect the light conversion efficiency improvement effect due to the use of the light diffusing agent, but when the light diffusing agent is used in an amount greater than about When it is included in an amount of 20% by weight, there is a possibility that quantum dots may be precipitated.

[Other additives]

For the improvement of stability and dispersibility of quantum dots, the non-solvent curable composition according to an embodiment may further include a polymerization inhibitor.

The polymerization inhibitor may include a hydroquinone-based compound, a catechol-based compound, or a combination thereof, but is not necessarily limited thereto. When the non-solvent-based curable composition according to an embodiment further includes a hydroquinone-based compound, a catechol-based compound, or a combination thereof, room temperature crosslinking during exposure after coating the non-solvent-based curable composition can be prevented.

For example, the hydroquinone-based compound, catechol-based compound, or a combination thereof may be hydroquinone, methylhydroquinone, methoxyhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,5 -Bis(1,1-dimethylbutyl)hydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl)hydroquinone, catechol, tert-butylcatechol, 4-Methoxyphenol, pyrogallol, 2,6-di-tert-butyl-4-methylphenol, 2-naphthol, tris(N-hydroxy-N-nitrosophenylamine) -O,O')aluminum (tris(N-hydroxy-N-nitrosophenylaminato-O,O')aluminum) or a combination thereof, but not necessarily limited thereto.

The hydroquinone-based compound, the catechol-based compound, or a combination thereof can be used in the form of a dispersion. The polymerization inhibitor in the form of a dispersion may be included in an amount of about 0.001% to about 3% by weight, eg, about 0.1% to about 2% by weight, based on the total amount of the non-solvent curable composition. When the polymerization inhibitor is included in the range, the time-lapse problem at room temperature can be solved and at the same time, the deterioration of sensitivity and the phenomenon of surface delamination can be prevented. That is, when the polymerization inhibitor is included in the range, the room temperature stability of the non-solvent-type curable composition can be improved, and the decrease in curing sensitivity and the delamination of the coating layer can be reduced or prevented.

In addition, the non-solvent curable composition according to an embodiment may further comprise malonic acid; 3-amino-1,2-propanediol; silane-based coupling agent; leveling agent; fluorine-based surfactant or a combination thereof, to Improved heat resistance and reliability.

For example, the non-solvent-based curable composition according to the embodiment may further comprise a silane having reactive substituents such as vinyl groups, carboxyl groups, methacryloxy groups, isocyanate groups, epoxy groups, and the like like coupling agent to improve the intimate contact characteristics with the substrate.

Examples of the silane-based coupling agent may be trimethoxysilylbenzoic acid, γ-methacrylpropoxytrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyl Triethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-epoxycyclohexylethyltrimethoxysilane, and the like, and these may be alone or in mixtures of two or more form use.

The silane-based coupling agent may be used in an amount of about 0.01 parts by weight to about 10 parts by weight based on 100 parts by weight of the non-solvent curable composition. When the silane-based coupling agent is included in the range, the close contact characteristic, storage ability, and the like are excellent.

In addition, the non-solvent-type curable composition may further contain a surfactant, such as a fluorine-based surfactant as needed, to improve coating properties and suppress the generation of spots, ie, improve leveling performance.

The fluorosurfactant may have a low weight average molecular weight of about 4,000 g/mole to about 10,000 g/mole, and particularly about 6,000 g/mole to about 10,000 g/mole. In addition, the fluorosurfactant may have a surface tension of 18 millinewtons/meter (mN/m) to 23 millinewtons/meter (in a 0.1% polyethyleneglycol monomethylether acetate (PGMEA) solution) measured in). When the fluorosurfactant has a weight average molecular weight and surface tension in the range, leveling properties can be further improved and excellent characteristics can be provided when applied to slit coating which is high-speed coating, because Spotting is prevented during coating and vapor generation is suppressed with fewer film defects. That is, when the weight-average molecular weight and surface tension of the fluorine-based surfactant are within the above-mentioned ranges, the leveling performance can be further improved, and when high-speed slit coating is used for coating, the generation of spots and the occurrence of spots can be reduced or prevented. Vapor generation, thereby reducing film defects.

和BM-

(BM化学公司(BM ChemieInc.))；MEGAFACE F

MEGAFACE F

MEGAFACE F

以及MEGAFACE F

(大日本油墨化学工业株式会社(Dainippon Ink Kagaku Kogyo Co.,Ltd.))；FULORAD FC-

FULORAD FC-

FULORAD FC-

以及FULORAD FC-

(住友3M株式会社(Sumitomo3M Co.,Ltd.))；SURFLON S-

SURFLON S-

SURFLON S-

SURFLON S-

以及SURFLON S-

(旭硝子株式会社(ASAHI Glass Co.,Ltd.))；以及SH-

SH-

SH-

SZ-

以及SF-

及类似物(东丽株式会社(Toray Silicone Co.,Ltd.))；迪爱生股份有限公司(DIC Co.,Ltd.)的F-482、F-484、F-478、F-554以及类似产品。An example of a fluorosurfactant may be BM-

and BM-

(BM Chemie Inc.); MEGAFACE F

MEGAFACE F

MEGAFACE F

and MEGAFACE F

(Dainippon Ink Kagaku Kogyo Co., Ltd.); FULORAD FC-

FULORAD FC-

FULORAD FC-

and FULORAD FC-

(Sumitomo3M Co., Ltd.); SURFLON S-

SURFLON S-

SURFLON S-

SURFLON S-

and SURFLON S-

(ASAHI Glass Co., Ltd.); and SH-

SH-

SH-

SZ-

and SF-

and the like (Toray Silicone Co., Ltd.); F-482, F-484, F-478, F-554 of DIC Co., Ltd. and similar product.

In addition, the non-solvent-based curable composition according to an embodiment may include a silicone-based surfactant in addition to the fluorine-based surfactant. Specific examples of the silicone-based surfactant may be TSF400, TSF401, TSF410, TSF4440 and the like from Toshiba silicone Co., Ltd., but are not limited thereto.

The surfactant may be included in an amount of about 0.01 parts by weight to about 5 parts by weight, eg, about 0.1 parts by weight to about 2 parts by weight, based on 100 parts by weight of the non-solvent curable composition. When the surfactant is included in the range, foreign substances are less generated in the non-solvent type curable composition.

In addition, the non-solvent-type curable composition according to an embodiment may further contain other additives such as antioxidants, stabilizers, and the like in predetermined amounts unless the characteristics are deteriorated (when these additives are contained).

Another embodiment provides a solvent-based curable composition comprising the aforementioned quantum dots (surface-modified quantum dots), a binder resin, and a solvent.

[binder resin]

The binder resin may include acryl-based resin, cardox-based resin, epoxy resin, or a combination thereof.

The acryl-based resin is a copolymer of a first ethylenic unsaturated monomer and a second ethylenic unsaturated monomer that are copolymerizable with each other, and may be a resin containing at least one acryl-based repeating unit.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and examples of the monomer include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid or a combination thereof.

The first ethylenically unsaturated monomer may be included in an amount of about 5 wt % to about 50 wt %, eg, about 10 wt % to about 40 wt %, based on the total amount of the acryl-based binder resin.

The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, vinylbenzyl methyl ether and the like; unsaturated carboxylate compounds such as Methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth)acrylate Benzyl acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate and the like; amino alkyl carboxylate ester compounds such as 2-amino (meth)acrylate Ethyl esters, 2-dimethylaminoethyl (meth)acrylate and the like; vinyl carboxylates such as vinyl acetate, vinyl benzoate and the like; glycidyl unsaturated carboxylate compounds such as (methyl) base) glycidyl acrylate and the like; vinyl cyanide compounds such as (meth)acrylonitrile and the like; unsaturated amide compounds such as (meth)acrylamide and the like; and the like, alone or Used as a mixture of two or more.

Specific examples of the acryl-based binder resin may be polybenzylmethacrylate, (meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate /styrene copolymer, (meth)acrylic acid/benzyl methacrylate/2-hydroxyethyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene/methacrylic acid 2 -Hydroxyethyl ester copolymer and the like, but not limited thereto, and may be used alone or in a mixture of two or more.

The weight average molecular weight of the acryl-based binder resin may be about 5,000 g/mol to about 15,000 g/mol. When the acryl-based binder resin has a weight average molecular weight in the range, close contact properties (eg, adhesion) to a substrate, physical properties, and chemical properties are improved, and the viscosity of the solvent-based curable composition is appropriate (appropriate) (eg suitable).

The cardox-based resin may include a repeating unit represented by Chemical Formula 16.

[Chemical formula 16]

In Chemical Formula 16,

R ³¹ and R ³² are each independently a hydrogen atom or a substituted or unsubstituted (meth)acryloyloxy alkyl group,

R ³³ and R ³⁴ are each independently a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and

Z ¹ is a single bond, O, CO, SO ₂ , CR ³⁵ R ³⁶ , SiR ³⁷ R ³⁸ (wherein, R ³⁵ to R ³⁸ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group) , or one of the linking groups represented by Chemical Formula 16-1 to Chemical Formula 16-11.

[Chemical formula 16-1]

[Chemical formula 16-2]

[Chemical formula 16-3]

[Chemical formula 16-4]

[Chemical formula 16-5]

In Chemical Equation 16-5,

R ^a is a hydrogen atom, ethyl, C ₂ H ₄ Cl, C ₂ H ₄ OH, CH ₂ CH=CH ₂ or phenyl.

[Chemical formula 16-6]

[Chemical formula 16-7]

[Chemical formula 16-8]

[Chemical formula 16-9]

[Chemical formula 16-10]

[Chemical formula 16-11]

Z ² is an acid anhydride residue, and

t1 and t2 are each independently an integer between 0 and 4.

The weight average molecular weight of the cardox-based binder resin may be about 500 g/mol to about 50,000 g/mol, eg, about 1,000 g/mol to about 30,000 g/mol. When the weight average molecular weight of the cardox-based binder resin is within the range, a satisfactory pattern can be formed without residues during manufacture of the cured layer, and the film thickness is not lost during development of the solvent-based curable composition.

The cardox-based binder resin may include a functional group represented by Chemical Formula 17 at at least one of the two terminals.

[Chemical formula 17]

In Chemical Formula 17,

Z ³ is represented by Chemical Formula 17-1 to Chemical Formula 17-7.

[Chemical formula 17-1]

In Chemical Formula 17-1, R ^b and R ^c are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group, or an ether group.

[Chemical formula 17-2]

[Chemical formula 17-3]

[Chemical formula 17-4]

[Chemical formula 17-5]

In Chemical Formula 17-5, R ^d is O, S, NH, substituted or unsubstituted C1 to C20 alkylene, C1 to C20 alkylamino, or C2 to C20 alkenylamino.

[Chemical formula 17-6]

[Chemical formula 17-7]

The cardox-based resin can be prepared, for example, by mixing at least two of the following: a fluorene-containing compound such as 9,9-bis(4-oxiranylmethoxyphenyl)fluorene(9,9-bis( 4-oxiranylmethoxyphenyl)fluorene); anhydride compounds, such as pyromellitic dianhydride, naphthalene tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, Cyclobutanetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, tetrahydrofurantetracarboxylic dianhydride and tetrahydrophthalic anhydride; glycol compounds such as ethylene glycol, propylene glycol and polyethylene glycol; alcohol compounds such as methanol, Ethanol, propanol, n-butanol, cyclohexanol and benzyl alcohol; solvent compounds such as propylene glycol methyl ethyl acetate and N-methylpyrrolidone; phosphorus compounds such as triphenylphosphine; and amines ) or an ammonium salt compound such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine or benzyltriethylammonium chloride.

When the binder resin is a cardox-based resin, a solvent-based curable composition (especially a photosensitive resin composition) containing the cardox-based resin has excellent developability and sensitivity during photocuring, and thus has Excellent fine patterning ability.

The acid value of the acryl-based resin may be about 80 milligrams potassium hydroxide/gram (mgKOH/g) to about 130 milligrams potassium hydroxide/gram. Excellent pixel resolution can be obtained when the acrylic resin has an acid value in the range.

Epoxy resins may be thermally polymerizable monomers or oligomers, and may contain compounds having carbon-carbon unsaturated bonds and carbon-carbon cyclic bonds.

The epoxy resins may include bisphenol A epoxy resins, bisphenol F epoxy resins, phenol novolac epoxy resins, cyclic aliphatic epoxy resins, and aliphatic polyglycidyl ethers, but need not be limited to this.

Commercially available products of the compound may be biphenyl epoxy resins such as YX4000, YX4000H, YL6121H, YL6640 or YL6677 from YukaShell Epoxy Co.; cresol novolac epoxy resins such as Japanese EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 from Nippon Kayaku Co. Ltd. and EPIKOTE 180S75 from Shell Epoxy Co., Ltd. and similar products ; Bisphenol A epoxy resins, such as EPIKOTE 1001, EPIKOTE 1002, EPIKOTE 1003, EPIKOTE 1004, EPIKOTE 1007, EPIKOTE 1009, EPIKOTE 1010, and EPIKOTE 828 from Shell Epoxies; Bisphenol F epoxy resins, such as oil EPIKOTE 807 and EPIKOTE 834 from Shell Epoxy Resins; Phenol novolac epoxy resins, such as EPIKOTE 152, EPIKOTE 154 or EPIKOTE 157H65 from Shell Epoxies and EPPN 201, EPPN 202 from Nippon Kayaku Co., Ltd. ; Cyclic aliphatic epoxy resins, such as CY175, CY177 and CY179 from CIBA-GEIGY A.GCorp., ERL-4234, ERL-4299, ERL from U.C.C. -4221 and ERL-4206, Showdyne 509 from Showa Denko K.K., Araldite CY-182 from Ciba-Geiky Group Corporation, CY-192 from Dainippon Ink & Chemicals Inc. and CY-184, EPICLON 200 and EPICLON 400 from Shell Epoxy Resins, EPIKOTE 871, EPIKOTE 872 and EP1032H60, ED-5661 and ED-5662 from Celanese Coating Corporation; Aliphatic Polyglycidyl Ethers , which can be EPIKOTE 190P and EPIKOTE 191P from Shell Epoxy Resin Company, EPOLITE 100MF from Kyoeisha Yushi Kagaku Kogyo Co., Ltd., EPOLITE 100MF from Nihon Yushi K.K. EPIOL TMP and similar products.

[solvent]

Solvent alcohols may include, for example, alcohols, such as methanol, ethanol, and the like; glycol ethers, such as ethylene glycol methyl ether, ethylene glycol ethyl ether, propylene glycol methyl ether, and the like; cellosolve acetate, such as acetic acid methyl cellosolve acetate, ethyl cellosolve acetate, diethyl cellosolve acetate, and the like; carbitols such as methyl ethyl carbitol, diethyl carbitol Alcohols, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and the like; propylene glycol alkyl ether acetates , such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate and the like; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl- n-acetone, methyl-n-butanone, methyl-n-amylketone, 2-heptanone and the like; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate Esters, isobutyl acetate, and the like; lactate esters, such as methyl lactate, ethyl lactate, and the like; alkyl glycolates, such as methyl glycolate, ethyl glycolate, butyl glycolate, and the like ; Alkoxyalkyl acetates such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate and the like; 3- Alkyl hydroxypropionate, such as methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, and the like; alkyl 3-alkoxypropionate, such as methyl 3-methoxypropionate, 3 - Ethyl methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate and the like; alkyl 2-hydroxypropionate, such as methyl 2-hydroxypropionate, Ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, and the like; alkyl 2-alkoxypropionate, such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate , ethyl 2-ethoxy propionate, methyl 2-ethoxy propionate and the like; alkyl 2-hydroxy-2-methyl propionate, such as methyl 2-hydroxy-2-methyl propionate esters, ethyl 2-hydroxy-2-methylpropionate and the like; 2-alkoxy-2-methylpropionate alkyl esters such as methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate and the like; esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, 2-hydroxyethyl propionate - methyl 3-methylbutyrate and the like; or ketoesters such as ethyl pyruvate and the like, and in addition the solvent alcohol may be N-methylformamide, N,N-dimethylformamide , N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ether, dihexyl ether, acetylacetone , isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate ( diet hyl oxalate), diethyl maleate, gamma-butyrolactone, ethylenecarbonate, propylene carbonate, phenyl cellosolveacetate, and the like, but not limited to this.

For example, the solvent may desirably be glycol ethers such as ethylene glycol monoethyl ether, ethylene diglycol methyl ethyl ether and the like; ethylene glycol alkyl ether acetates such as ethyl acetate ethyl cellosolve acetate and the like; esters such as 2-hydroxy propionate ethyl ester and the like; carbitols such as diethylene glycol monomethyl ether and the like; propylene glycol alkyl ether acetate, Such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate and the like; alcohols such as ethanol and the like; or combinations thereof.

For example, the solvent can be a polar solvent, including propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethanol, ethylene glycol dimethyl ether, ethylenediglycol methyl ethyl ether, diethyl ether Glycol dimethyl ether, 2-butoxyethanol, N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, gamma-butyrolactone, or a combination thereof.

The solvent may be included in an amount of about 20% to about 80% by weight, eg, about 35% to about 80% by weight, based on the total amount of the solvent-borne curable composition. When the solvent is within the range, the solvent-based curable composition has an appropriate viscosity, and thus can have excellent coating characteristics in large-area coating by spin coating and slot coating.

For example, the solvent-based curable composition may further include at least one of a monomer having a carbon-carbon double bond at the terminal, a polymerization initiator, a diffusing agent, and other additives.

For example, the solvent-based curable composition may be a photosensitive resin composition. In this case, the solvent-type curable composition may contain a photopolymerization initiator as a polymerization initiator.

Another embodiment provides a cured layer manufactured using the aforementioned non-solvent-based curable composition and solvent-based curable composition, a color filter including the cured layer, and a display device including the color filter.

One of the methods of manufacturing the cured layer may include applying the aforementioned non-solvent-based curable composition and/or solvent-based curable composition on a substrate using an ink jet spray method to form a pattern (S1); and curing the pattern (S2). Curing can be photocuring or thermal curing.

(S1) Formation of Pattern

The non-solvent curable composition can be applied to the substrate in an ink jet spray process, desirably from about 0.5 microns to about 20 microns. The inkjet spraying method can form a pattern by spraying a single color from each nozzle and thus repeating the spraying multiple times according to the desired number of colors, but to reduce the process, the pattern can be formed by simultaneously spraying the desired number of colors through each inkjet nozzle . That is, a pattern can be formed by simultaneously ejecting a desired number of colors (eg, each containing one color) from a plurality of nozzles.

(S2) Curing

The resulting pattern is cured to obtain pixels. Here, the curing method may be a thermal curing process or a light curing process. The thermal curing process can be performed at greater than or equal to about 100°C, desirably in the range of about 100°C to about 300°C, and more desirably in the range of about 160°C to about 250°C. The photocuring process may comprise radiating actinic radiation, such as UV radiation at about 190 nanometers to about 450 nanometers, eg, about 200 nanometers to about 500 nanometers. Irradiation is carried out by using light sources such as mercury lamps with low pressure, high pressure or extra high pressure, metal halide lamps, argon lasers and the like. X-rays, electron beams, and the like can also be used as desired.

Other methods of manufacturing the cured layer may include manufacturing the cured layer by the following photolithography method using the aforementioned non-solvent-based curable composition and/or solvent-based curable composition.

(1) Coating and film formation

Coating the aforementioned curable resin composition to a desired thickness on a substrate subjected to a predetermined pretreatment using a spin coating method or a slit coating method, a roll coating method, a screen printing method, a painting method and the like, For example, a thickness of from about 2 microns to about 10 microns. Next, the coated substrate is heated at a temperature of about 70°C to about 90°C for 1 minute to 10 minutes to remove the solvent and form a film.

(2) Exposure

After placing a mask having a predetermined shape, the resulting film is irradiated with actinic rays such as UV rays of about 190 nm to about 450 nm, eg, about 200 nm to about 500 nm, to form a desired pattern. Irradiation is carried out by using light sources such as mercury lamps with low pressure, high pressure or extra high pressure, metal halide lamps, argon lasers and the like. X-rays, electron beams, and the like can also be used as desired.

When using a high pressure mercury lamp, the exposure process uses, for example, a light dose of 500 millijoules per square centimeter (mJ/cm ² ) or less than 500 millijoules per square centimeter (with a 365 nanometer sensor). However, the light dose may vary depending on the kind of each component of the curable composition, the combination ratio thereof, and the dry film thickness.

(3) Development

After the exposure process, an alkaline aqueous solution is used to develop the exposed film by dissolving and removing unnecessary parts other than the exposed parts, thereby forming an image pattern. In other words, when the alkaline developing solution is used for development, the non-exposed areas are dissolved and an image color filter pattern is formed.

(4) Post-processing

The developed image pattern can be reheated or irradiated by actinic rays and the like to be cured to achieve thermal resistance, light resistance, intimate contact characteristics, crack resistance, chemical resistance, high strength, storage stability and the like Excellent quality of characteristics.

In the following, the present invention is shown in more detail with reference to examples. However, these examples are not to be construed as limiting the scope of the present invention in any sense.

(Preparation of Surface Modified Quantum Dot Dispersion)

Preparation Example 1

A magnetic rod was put into a 3-neck round-bottomed round flask, and a quantum dot-cyclohexyl acetate (CHA) solution (solid content: 26 to 27 wt%) was weighed and added to the round-bottomed round in the flask. The compound represented by Chemical Formula A is added thereto.

(Synthesis method of chemical formula A: 50 g of thioglycolic acid, 91 g of 2-[2-(2-methoxyethoxy)ethoxy]-ethanol and 10.27 g of p-toluenesulfonic acid mono The hydrate was placed in a flask and then uniformly dispersed in 500 mL of cyclohexane under nitrogen atmosphere. The injection hole of the flask was connected to a dean stark, and a condenser was connected to the dean stark. Enstark. The reaction flask was stirred for a predetermined time while heating at 80°C, and then the interior of the Deenstark was checked for water accumulation. After water accumulation was determined, stirring was performed for an additional 12 hours. When 0.54 moles of water appeared , the reaction was complete. Ethyl acetate and excess water were added to the reactants for extraction and neutralization, a vacuum evaporator was used for concentration, and the final product therefrom was then dried in a vacuum oven.)

The mixture was mixed well for 1 minute and then stirred at 80°C under nitrogen atmosphere. When the reaction was completed, the resultant was cooled to room temperature, and the quantum dot reaction solution was added to cyclohexane to obtain a precipitate. The precipitated quantum dot powder was separated from cyclohexane by centrifugation. The clear solution was decanted and discarded, and the precipitate was then thoroughly dried in a vacuum oven for one day to obtain surface-modified quantum dots.

The surface-modified quantum dots were stirred with a monomer represented by Chemical Formula 15-1 (triethylene glycol dimethacrylate, Miwon Commercial Co., Ltd.) for 12 hours to obtain surface modification Quantum dot dispersion.

[Chemical formula A]

[Chemical formula 15-1]

Preparation Example 2

A surface-modified quantum dot dispersion liquid was obtained according to the same method as Preparation Example 1, except that the compound represented by Chemical Formula E was used in place of the compound represented by Chemical Formula A.

(Synthesis method of chemical formula E: 79 g of p-toluenesulfonyl chloride and 150 ml of THF dispersion were slowly injected into 100 g of pentaethylene glycol monomethyl ether, 14.3 g of NaOH, 500 ml of THF and 100 ml of H at ₀ °C In a mixed solution of O. After 30 minutes, the injection was completed, and the resulting mixture was stirred for about 12 hours. When the reaction was completed, the resultant was purified by extraction, neutralization, and concentration, and then fully dried in a vacuum oven. The resultant The product was placed in a flask and dissolved in ethanol under nitrogen atmosphere. Thiourea was added in 3 to 5 equivalents, and then stirred at 100° C. for 12 hours. 20 equiv of NaOH dilution was injected into the reactants, and It was then stirred for another 5 hours. When the reaction was complete, the resultant was washed, extracted and neutralized several times with water and diluents of hydrochloric acid, and then concentrated and fully dried in a vacuum oven to obtain the product.)

[chemical formula E]

Preparation Example 3

A surface-modified quantum dot dispersion liquid was obtained according to the same method as Preparation Example 1, except that the compound represented by Chemical Formula K was used in place of the compound represented by Chemical Formula A.

(Synthesis method of chemical formula K: 260 g of PH-4 (Hannon Chemicals Inc.) and 140 g of allylsuccinic anhydride were stirred at 80° C. for 20 hours.)

[Chemical formula K]

Preparation Example 4

Surface-modified quantum dots were obtained according to the same method as Preparation Example 1, except that the monomer represented by Chemical Formula 15-3 (butyl dimethacrylate, Hannong Chemical Co., Ltd.) was used instead of the monomer represented by Chemical Formula 15-1 Dispersions.

[Chemical formula 15-3]

Comparative Preparation Example 1

According to the same procedure as in Preparation Example 1, except that a monomer having no carbon-carbon double bond at the terminal, OXT 221 (Toagosei Co., Ltd.) was used instead of the monomer represented by Chemical Formula 15-1 Methods The surface-modified quantum dot dispersion was obtained.

Assessment 1: Dispersion

The particle size of each quantum dot dispersion liquid according to Preparation Example 1 to Preparation Example 4 and Comparative Preparation Example 1 was measured three times by using a microparticle size analyzer to obtain an average particle size, and the results are shown in Table 1.

(Table 1)

Particle size (nm) Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Comparative Preparation Example 1 D50 12.4 12.5 12.2 12.8 21.1 D90 36.6 38 24.6 28.9 48.2

Referring to Table 1, each of the quantum dot dispersions according to Preparation Example 1 to Preparation Example 4 exhibited a narrow particle distribution, which showed that the quantum dots were well dispersed in the solvent of high boiling point and high surface tension, but according to Comparative Preparation Example The quantum dot dispersion of 1 exhibits a broad particle distribution, which indicates that the quantum dots are not well dispersed in the high boiling point and high surface tension solvent.

(Preparation of non-solvent curable composition)

Example 1

The dispersion liquid according to Preparation Example 1 was weighed, and then mixed and diluted with the monomer represented by Chemical Formula 15-1, and a polymerization inhibitor (methylhydroquinone, Tokyo Chemical Industry Co., Ltd.); 5% by weight) and then stirred for 5 minutes. Subsequently, a photoinitiator (TPO-L, available from Polynetron Co., Ltd.) was injected thereinto, and a light diffusing agent (TiO ₂ ; SDT89, available from Iridos Co., Ltd.) was added thereto. ). The entire dispersion was stirred for 1 hour to prepare a non-solvent curable composition. 8% by weight of quantum dots, 80% by weight of the monomer represented by Chemical Formula 15-1, 1% by weight of polymerization inhibitor, 3% by weight of photoinitiator, based on the total amount of the non-solvent curable composition agent and 8% by weight of light diffusing agent.

Example 2

A non-solvent-type curable composition was prepared according to the same method as in Example 1, except that the dispersion liquid according to Preparation Example 2 was used in place of the dispersion liquid according to Preparation Example 1.

Example 3

A non-solvent curable composition was prepared according to the same method as in Example 1, except that the dispersion liquid according to Preparation Example 3 was used in place of the dispersion liquid according to Preparation Example 1.

Example 4

A non-solvent was prepared according to the same method as Example 1, except that the dispersion liquid according to Preparation Example 4 was used in place of the dispersion liquid according to Preparation Example 1 and the monomer represented by Chemical Formula 15-3 was used instead of the monomer represented by Chemical Formula 15-1 type curable composition.

Example 5

Except based on the total amount of the non-solvent curable composition, 48 wt % of quantum dots, 40 wt % of the monomer represented by Chemical Formula 15-1, 1 wt % of a polymerization inhibitor, 3 wt % of a photogenic A non-solvent type curable composition was prepared according to the same method as in Example 2 except for the starting agent and 8% by weight of the light diffusing agent.

Comparative Example 1

Except that the dispersion liquid of Comparative Preparation Example 1 was used in place of the dispersion liquid of Preparation Example 1 and a monomer having no carbon-carbon double bond at the terminal was used, OXT 221 (Toagosei Co., Ltd.) was used instead of the monomer represented by Chemical Formula 15-1 Otherwise, according to the same method as Example 1, a non-solvent type curable composition was prepared.

Comparative Example 2

Except based on the total amount of the non-solvent curable composition, 50 wt % of quantum dots, 38 wt % of the monomer represented by Chemical Formula 15-1, 1 wt % of a polymerization inhibitor, 3 wt % of a photopolymer are used A solvent-free curable composition was prepared according to the same method as in Example 2 except for the starting agent and 8% by weight of a light diffusing agent.

Comparative Example 3

Except based on the total amount of the non-solvent-based curable composition, 6 wt % of quantum dots, 82 wt % of the monomer represented by Chemical Formula 15-1, 1 wt % of a polymerization inhibitor, 3 wt % of photogenic A solvent-free curable composition was prepared according to the same method as in Example 2 except for the starting agent and 8% by weight of a light diffusing agent.

Evaluation 2: Evaluation of Optical Characteristics

Glass substrates (G-1, G-2) were coated with a spin coater (800 revolutions per minute (rpm), 5 seconds, Opticoat MS-A150, Mikasa Co., Ltd.) ) or yellow photoresist (YPR) (Y-1, Y-2) to coat each of the compositions according to Examples 1 to 5 and Comparative Examples 1 to 3 to a thickness of about 15 microns, And it was exposed with a 395 nm UV exposure device at 5000 mJ/cm2 (83° C., 10 sec) under nitrogen atmosphere. Subsequently, each 2 cm x 2 cm single film sample was loaded in an integrating sphere apparatus (QE-2100, Otsuka Electronics, Co., Ltd.) and the light absorption rate and light efficiency were measured, And the results are shown in Tables 2 to 9.

(Table 2)

(table 3)

(Table 4)

(table 5)

(Table 6)

(Table 7)

(Table 8)

(Table 9)

Evaluation 3: Emission rate of non-solvent curable compositions as a function of incubation time

The discharge rate depending on the latency time of each of the non-solvent-based curable compositions according to Examples 1 to 5 and Comparative Examples 1 to 3 was evaluated in the following method, and the results show in Table 10.

The non-solvent-based curable composition was sprayed through 100 nozzles on the inkjet apparatus and dropped onto the pixels of the substrate, respectively, and then stopped and left as it was. Subsequently, when the non-solvent-type curable composition was sprayed through a predetermined time (latency time) unit, the number of nozzles that were not clogged but sufficiently discharged was counted. That is, after a set time or a predetermined time (latency time) has elapsed from the time when the initial spray of the non-solvent curable composition was stopped, the number of nozzles that remained unclogged was counted.

(Table 10)

(Number of Units)

Evaluation 4: Room temperature (25°C) storage stability of non-solvent curable composition

The room temperature storage stability (storagestability) depending on the incubation time of the non-solvent-based curable compositions according to Examples 1 to 5 and Comparative Examples 1 to 3 was evaluated by calculating the viscosity difference from the initial viscosity after the elapse of time , and the results are shown in Table 11. That is, the storage stability at room temperature is represented by the change in viscosity with respect to the initial viscosity with storage time.

The viscosity was measured by using a viscometer (RheoStress 6000, HAAKE Technik GmbH) at room temperature for 2 minutes at 100 rpm.

(Table 11)

(Unit: centipoise)

Referring to Evaluation 1 to Evaluation 4, the non-solvent-based curable compositions according to the Examples had appropriately adjusted viscosity for ink jetting and exhibited very excellent optical characteristics. In addition, the storage stability is also excellent at room temperature.

(Preparation of Solvent-Based Curable Composition)

Example 6

The dispersion liquid according to Preparation Example 1 was weighed to disperse quantum dots (23 wt %) in dimethyl adipate (45 wt %) and mixed with a cardox-based binder resin (TSR-TA01, TAKOMA) (8 wt %) to prepare a quantum dot dispersion. Subsequently, as thermosetting monomers, OXT-221 (Toagosei Co., Ltd.) (1 wt %) and PFM-02 (SMS) (16.5 wt %), a light diffusing agent (TiO ₂ ; SDT89, Iridos Co., Ltd.) were mixed (2% by weight), ethylene glycol di-3-mercaptopropionate (Bruno BockChemische Fabrik GMBH & CO., KG) (4.2% by weight) and methyl hydrogen as a polymerization inhibitor Quinone (Tokyo Chemical Industry Co., Ltd. (TCI)) (0.3% by weight) was mixed, and the quantum dot dispersion liquid was added thereto, and then stirred to prepare a solvent-based curable composition.

Example 7

The following components were used in corresponding amounts to prepare a solvent-based curable composition (photosensitive resin composition).

Specifically, the photopolymerization initiator was dissolved in the solvent, and the solution was sufficiently stirred at room temperature for 2 hours. Subsequently, the binder resin together with the photoconversion material and the dispersant (TEGO D685 manufactured by EVONIK) were added thereto, and the resulting mixture was stirred again at room temperature for 2 hours. Next, a diffusing agent and a fluorine-based surfactant were added thereto, and then stirred at room temperature for 1 hour, and the product therein was filtered three times to remove impurities and prepare a photosensitive resin composition.

1) Quantum dots: 12% by weight of quantum dots obtained from Preparation Example 1

2) Binder resin: 25% by weight cardo-based binder resin (TSR-TA01, Tacoma)

3) Polymerizable monomer: 5.4% by weight pentaerythritol hexamethacrylate (DPHA, Nippon Kayaku Co., Ltd.)

4) Photopolymerization initiator: 0.7% by weight of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO, Sigma-Aldrich Corporation)

5) Solvent: 39% by weight of dimethyl adipate

6) Diffusion agent: 39% by weight titanium dioxide dispersion ( _TiO2 solid content: 20% by weight, average particle size: 200 nm, Ditto Technology)

7) Thiol additive: 2 wt% ethylene glycol di-3-mercaptopropionate (BRUNO BOCK)

8) Other additives: 0.9% by weight of fluorine-based surfactant (F-554, Diaisheng Co., Ltd.)

Evaluation 5: Photoconversion Ratio and Photoconversion Maintenance Ratio of Quantum Dots

The curable compositions according to Example 6 and Example 7, respectively, were coated on glass substrates to a thickness of 2 μm with a spin coater (150 rpm, Optical Coating MS-A150, Mikasa Co., Ltd.), and then at 80° C. The lower hot plate was dried for 1 minute to obtain a short film, and its initial blue light conversion was measured (first step).

The resulting film was dried in a forced convection dryer at 220°C for 40 minutes, and its blue light conversion was measured (second step).

In the first and second steps, the photoconversion ratio and photoconversion maintenance ratio of incident blue light from the BLU to green were evaluated, and the results are shown in Table 12. In this paper, blue light conversion (green/blue) was measured by using a CAS 140CT spectrometer, and specifically, bare glass was placed on a blue BLU (455 nm) covered with a scattering film to first obtain with a detector For reference, each short film coated with the solvent-borne curable composition according to Examples 6 to 7 was placed and the increase in peak converted to green light relative to the decrease in blue absorption peak was calculated. That is, the light conversion rate is calculated as the ratio of the increase in the peak height of green light to the decrease in the peak height of blue light in the absorption spectrum on a blue BLU (455 nm) covered with a scattering film based on bare glass . In addition, how much the light conversion rate in the first step was maintained in the second step, that is, the light conversion maintenance rate from the first step to the second step was also measured, and the results are shown in Table 12.

In addition, for the solvent-based curable composition of Example 7, after irradiating UV with a power supply of 100 mJ/cm 2 , a post-baking (post-baking) was performed in a convection cleaning oven (Jongro) at 180° C. baking; POB) for 30 minutes. The light conversion rate was measured with an exposure device (ghi broadband, Ushio Inc.), and the results are shown in Table 13.

(Table 12)

(unit:%)

Example 6 Example 7 light conversion rate 28 25 light conversion maintenance 95 93

(Table 13)

(unit:%)

Example 7 Initial light conversion rate 25 Photoconversion after a 30-min POB at 180°C 21.8

As shown in Table 12 and Table 13, the solvent-based curable compositions prepared using the surface-modified quantum dots according to the examples exhibited less degraded blue light conversion due to the color filter process, but higher light conversion maintenance rate.

While this invention has been described in connection with what are presently considered to be practical example embodiments, it is to be understood that this invention is not limited to the disclosed embodiments, but on the contrary, this invention is intended to cover the spirit and scope of the appended claims Various modifications and equivalent arrangements within. Accordingly, the foregoing embodiments should be understood to be illustrative and not limiting of the present invention in any way.

Claims (22)

1. A quantum dot surface-modified with one or a combination of compounds represented by chemical formulas 1 to 14:

[ chemical formula 1]

[ chemical formula 2]

[ chemical formula 3]

[ chemical formula 4]

[ chemical formula 5]

[ chemical formula 6]

Wherein, in chemical formulas 1 to 6,

R¹to R⁷Each independently a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,

L¹to L¹⁶Each independently a substituted or unsubstituted C1 to C10 alkylene group, and

n1 to n7 are each independently an integer of 0 to 10,

[ chemical formula 7]

[ chemical formula 8]

[ chemical formula 9]

Wherein, in chemical formulas 7 to 9,

R⁸and R⁹Each independently substituted or unsubstituted C1 to C10 alkyl,

L¹⁷to L²³Each independently a substituted or unsubstituted C1 to C10 alkylene group, and

n8 to n10 are each independently an integer of 0 to 10,

[ chemical formula 10]

[ chemical formula 11]

[ chemical formula 12]

[ chemical formula 13]

Wherein, in chemical formulas 10 to 13,

R¹⁰to R¹⁵Each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L²⁴to L²⁹Each independently a substituted or unsubstituted C1 to C10 alkylene group, and

n11 to n16 are each independently an integer of 0 to 10,

[ chemical formula 14]

Wherein, in chemical formula 14,

R¹⁶to R¹⁸Each independently substituted or unsubstituted C1 to C10 alkyl,

L³⁰to L³²Each independently a substituted or unsubstituted C1 to C10 alkylene group, and

n17 to n19 are each independently an integer of 0 to 10.

2. The quantum dot of claim 1, wherein the quantum dot has a maximum fluorescence emission wavelength of 500 to 680 nanometers.

3. A non-solvent based curable composition comprising

Quantum dots, and

a polymerizable monomer having a carbon-carbon double bond at a terminal,

wherein the polymerizable monomer is contained in an amount of 40 to 80% by weight based on the total amount of the non-solvent type curable composition.

4. The solventless curable composition according to claim 3 wherein the polymerizable monomer has a molecular weight of 220 to 1,000 g/mole.

5. The non-solvent type curable composition according to claim 3, wherein the polymerizable monomer is represented by chemical formula 15:

[ chemical formula 15]

Wherein, in chemical formula 15,

R¹⁹and R²⁰Each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L³³and L³⁵Each independently a substituted or unsubstituted C1 to C10 alkylene group, and

L³⁴is a substituted or unsubstituted C1 to C10 alkylene or ether group.

6. The solventless curable composition of claim 3 wherein the solventless curable composition further comprises a polymerization initiator, a light diffuser, or a combination thereof.

7. The non-solvent borne curable composition according to claim 6, wherein the light diffuser comprises barium sulfate, calcium carbonate, titanium dioxide, zirconium oxide, or a combination thereof.

8. The solventless curable composition of claim 6 wherein the solventless curable composition further comprises a polymerization inhibitor; malonic acid; 3-amino-1, 2-propanediol; a silane-based coupling agent; a leveling agent; a fluorine-based surfactant, or a combination thereof.

9. The non-solvent based curable composition according to claim 3, wherein the quantum dot is the quantum dot according to claim 1.

10. A solvent-borne curable composition comprising

The quantum dot of claim 1;

a binder resin; and

a solvent.

11. The solvent-borne curable composition according to claim 10, wherein the solvent-borne curable composition further comprises a polymerizable monomer, a polymerization initiator, a light diffuser, or a combination thereof.

12. The solvent-based curable composition according to claim 10, wherein the solvent-based curable composition is a photosensitive resin composition.

13. A cured layer made using the non-solvent based curable composition of claim 3.

14. A cured layer made using the solvent-borne curable composition of claim 10.

15. A color filter comprising the cured layer as defined in claim 13.

16. A color filter comprising the cured layer as defined in claim 14.

17. A display device comprising the color filter according to claim 15.

18. A display device comprising the color filter according to claim 16.

19. A method of making a cured layer comprising

Applying the non-solvent type curable composition according to claim 3 onto a substrate by an inkjet method to form a pattern; and

and curing the pattern.

20. A method of making a cured layer comprising

Applying the solvent-based curable composition of claim 10 to a substrate by an inkjet method to form a pattern; and

and curing the pattern.

21. A method of making a cured layer comprising

Applying the non-solvent type curable composition according to claim 3 onto a substrate by an inkjet method to form a pattern;

developing the pattern; and

and (6) heat treatment.

22. A method of making a cured layer comprising

Applying the solvent-based curable composition of claim 10 to a substrate by an inkjet method to form a pattern;

developing the pattern; and

and (6) heat treatment.